Coloring cellulose textile material with a cellulose{14 reactive dye

ABSTRACT

A process for colouring cellulose textile materials by impregnating the material with a water-soluble dye containing a cellulose-reactive group and fixing the dye on the material by treatment with an alkali applied in the dyebath or a separate bath in an amount conventionally used for that alkali for fixation of cellulose-reactive dyes, characterised in that the dyestuff used exhibits the following percentage exhaustions at different saline concentrations when dyed on to cotton or viscose rayon for 60 minutes at a strength of 0.5-1.0%, based on the weight of material being dyed, a liquor-to-goods ratio of 20:1 and a temperature of 80* C: g/l sodium chloride 0 20 40 60 80 100 120 exhaustion 0-15 40-80 55-86 65-90 71-94 75-96 78-97 AND THAT THE MATERIAL IS SUBJECTED AFTER FIXATION OF THE DYE TO AT MOST A RINSE IN WATER TO WASH OUT LOOSE DYESTUFF AND DYEBATH ADDITIVES.

United States Patent [191 Andrew et al.

[ June 11, 1974 [73] Imperial Chemical Industries Limited, London, England [22] Filed: Feb. 11, 1972 [2]] Appl. No.: 225,435

[30] I Foreign Appl i cation I iiority fiata Feb. 25. 1971 Great Britain ..5419/71 UIs. c'|...l 8754.2, 8/1 A, s/i 13' int. Cl D06p 3/66 Field of Search 8/54.2, 1.2, 1 E, 163

Assignee:

References Cited UNITED STATES PATENTS 10/1972 Ackermann et a1. 8/163 X OTHER PUBLICATIONS Colour Index, Vol. 3, 3rd Ed., 1971, pp. 3,463, 3,533, 3,534.

EXHAUSTION (I) Primary Examiner-Leon D. Rosdol Assistant Examiner-T. .1. Herbert, Jr.

Attorney, Agent, or Firm-Cushman, Darby & Cushman [57] ABSTRACT A process for colouring cellulose textile materials by impregnating the material with a water-soluble dye containing a cellulose-reactive group and fixing the dye on the material by treatment with an alkali applied in the dyebath or a separate bath in an amount conventionally used for that alkali for fixation of cellulose-reactive dyes, characterised in that the dyestuff used exhibits the following percentage exhaustions at different saline concentrations when dyed on to cotton or viscose rayon for 60 minutes at a strength of 0.5-1 .0%, based on the weight of material being dyed, a liquor-to-goods ratio of :1 and a temperature of 80 C: g/] sodium chloride 0 2O 80 100 120 ex- .thaustion O-15 40-80 55-86 -90 71-94 75-96 78-97 and that the material is subjected after fixation of the dye to at most a rinse in water to wash out loose dyestuff and dyebath additives.

2 Claims, 1 Drawing Figure I I I I NuCl /2) 1 v 2 COLORING CELLULOSE TEXTILE MATERIAL Portion l is used as a control" solution. Portions 2 8 WITH A CELLULOSE-REACIIVE DYE are used as dyebaths to dye g portions of eithercotton hanks or viscose rayon fabric. The solution is heated to This invention relates to a new colouration process then the erial is ed n dyed With uniand more particularly to a process for colouration of -5 form g tation, preferably in a laboratory dyeing macellulose textile materials with cellulose-reactive dyes. n After 60 minutes a 2 ml sample of the dye liquor is diluted to 50 ml with distilled water and the optical Cellulose-reactive dyes first became commercially n ity at XmaX is measured in a spectrophotometer available in 1956, but a comparatively large number and compared ith the optical density of a similarly dihave been developed commercially and made available 10 luted sampl f P r ion l- The difference in optical to the public since that date. All these dyestuffs contain density is e o Calculate the adsorption of dyestuff a sufficiency of sulphonic acid groups to make them in the usual way. water-soluble and at least one atom or group which is The class of dyestuffs suitable for use in the new dyecapable in the presence of an alkaline substance of reing process are those whose exhaustion on to cotton acting with the hydroxyl groups of cellulose so that the i5 and viscose rayon fibres when applied in this manner dyestuff, or the remainder of the dyestuff after splitting fall between the lines A and B of the drawing attached off of this atom or group, becomes covalently linked to to this specification. As can be seen from the drawing, the cellulose molecule. Dyestuff attached to the celluthe dyestuff used, within exhaustion curve limits A and lose in this manner is far more resistant to washing than B, exhibits the following percentage exhaustion for the the water-soluble direct dyes previously used but the following saline concentrations:

exhaustion: 0-15 40-80 55-86 65-90 7 l-94 75-96 79-94 methods of application used invariably cause some hy- Thus according to the present invention there is prodrolysis to an inert dyestuff which does not react with vided a process for colouring cellulose textile materials the cellulose molecule and would have poor fastness to which comprises treating the material in the presence washing if left in the material. From the advent of reacof aqueous alkali with a water-soluble cellulosetive dyes, therefore, it has been customary for materials reactive dyestuff of the class defined hereinbefore and dyed or printed with reactive dyestuffs to be thoroughly in subsequently processing the material to remove dyescoured at or near the boil with a solution of soap or debath additives, using at most a rinse with water for the tergent to remove the colouring matter which has not washing step. reacted with the cellulose. As stated above, cellulose-reactive dyestuffs must in contrast, direct dyes are usually finished off after contain an atom or group capable of reacting with the the colouring process by a rinse with warm water and hydroxyl groups of cellulose so that the dyestuff or its optionally a simple after treatment with a cationic residue become covalently linked to the cellulose moleagent or metallic salt to remove dyebath additives and cule. A large number of substituents containing such possibly a little dyestuff loosely attached to the surface groups are known from the literature on this subject, of the material being coloured. The additional scouring for example:' vinyl sulphone and aliphatic sulphone step customary with reactive dyes adds considerably to groups which contain a halogen atom or sulphate ester the cost of the process of dyeing with these dyes, but 40 groups in B-position to the sulphur atom, e.g. B-chloroto date has appeared to be indispensible. ethylor B-sulphatoethylsulphone and B-sulphatoethylit a no been found Possible, however, to define a sulphonylamino groups, a,B-unsaturated acyl radicals class of reactive dyestuffs for which the customary or aliphatic carboxylic acids for example, acrylic acid, scouring process can be dispensed With but yet g a-chloro-acrylic acid, propiolic acid, maleic acid and dyeings which are only slightly lower in fastness to monoand dichloro-maleic acids; also the acyl radicals washing and other wet treatments than commercially of acids which contain a substituent which reacts with available react dye but have a much higher h cellulose or polyamides in the presence of an alkali, e. g. than direct dyes. These dyes Offer a cha ae the radical of a halogenated aliphatic acid such as chlochange of substantivity in saline solutions of different roacetic acid, B-hl0roand B-bromo-propionic acids strengths when applied under the conditions defined a d a,fl-dihloroand dibromo-propionic a ids Oth r hereafter. The test conditions USCdlO define whether or examples of cellulose or p lyamide-reactlve groups are not a dyestuff is iuitablle are afsgos lol -f h d tetrafluorocyclobutane carbonyl, trifiuorocyclobutene 5 ml Portions 0 a $0 Uilon 0 g 0 t 8 P y carbonyl, tetrafluorocyclobutylethenyl carbonyl, trilfl 100 ml 0f distilled water are dllUllCCl according to the fluorocyclobuteneethenyl carbonyl, and heterocyclic following table: radicals which contain 2 or 3 nitrogen atoms in the heterocyclic ring and at least one celluloseor polyamidereactive substituent on a carbon atom of the ring. Portion 20% brine Water As examples of such heterocyclic radicals, there may (ml) (ml) be mentioned, for example I o 95 2:3-dichloro-quinoxalme-5- or -6-sulphonyl, 2 0 95 2:3-dichloro-quinoxaline-5- or -6-carbonyl, 3 I0 85 2:4-dichloro-quinazoline-6- or -7-sulphonyl, g8 22 2:4:6-trichloro-quinazoline-7- or -8-sulphonyl, 6 40 55 2:4:7- or 2:4:8-trichloro-quinazoline-6-sulphonyl, g 28 g; 2:4-dichloro-quinazoline-tS-carbonyl,

l :4-dichloro-phthalazine-6-carbonyl, 4:5-dichloro-pyridazon-l-yl,

3 2:4-dichloro-pyrimidine-5-carbonyl, l-(phenyl-4-carbonyl )-4 S-dichloro-pyridazone,

l-( phenyl-4-sulphonyl )-4 :S-dichloro-pyridazone,

and more particularly s-triazin-Z-yl and pyrimidin-2-yl or 4-yl radicals which contain an at least one of the remaining 2-, 4- and 6-positions, a bromine or, preferably, a chlorine atom, a sulphonic acid group, a thiocyanato group, an aryloxy or arylthio group containing an electronegative substituent such as sulphophenoxy, sulphophenylthio, nitrosulphophenoxy, disulphophenoxy and sulphonaphthoxy, or a group of the formula:

wherein Y represents a group of atoms necessary to form a or 6-membered heterocyclic ring which may carry substituents or form part of a fused ring system; or a quaternary ammonium e.g. pyridinium group; or a group of the formula:

wherein R and R each represent the same or different alkyl, cycloalkyl, aryl or aralkyl group, or R and R together form, together with the nitrogen atom, a 5- or 6-membered heterocyclic ring; or a group of the formula:

wherein R and R may be the same or different and each represents a hydrogen atom or an alkyl, aryl or aralkyl group.

ln the cases where the pyrimidine ring or triazine ring carries only one such reactive substituent, the said ring may have a non-reactive substituent on the remaining carbon atoms.

By a non-reactive substituent there is meant a group which is bound by a covalent bond to a carbon atom of the triazine or pyrimidine nucleus, which covalent bond is not ruptured under the conditions used for application of the reactive dye.

As examples of such substituents, there may be mentioned, for example, primary amino and hydroxyl groups, also monoor disubstituted amino groups, etherified hydroxyl and etherified mercapto groups; in the case of substituted amino groups, this class includes, for example, monoand di-alkylamino groups in which the alkyl groups preferably contain at most 4 carbon atoms, and which may also contain substituents for example. hydroxyl or alkoxy groups, and phenylamino and naphthylamino groups preferably containing sulphonic acid substituents; in the case of etherified hydroxyl and mercapto groups, this class includes, for example, alkoxy and alkylthio groups preferably those of low molecular weight, i.e. having up to 4 carbon atoms and phenoxy, phenylthio, naphthoxy or naphthylthio groups; as particular examples of all these classes there may be mentioned for example:

Methylamino,

and sulphocarboxy- N-w-sulphomethylphenylamino,

methoxy, ethoxy and butoxy,

phenoxy, methylphenoxy and chlorophenoxy and phenylthio groups. Chlorine atoms or cyano, nitro, carboxy and carbalkoxy groups in the 5-position of a pyrimidyl radical come into the category of non-reactive substituents.

Textile materials which may be dyed by the new process include cotton, viscose rayon, including polynosic and high wet modulus regenerated cellulose, linen and other essentially cellulosic fibres in the form of loose fibres, slivers, yarns, threads, woven, knitted, braided or otherwise interlaced, or unwoven sheet materials, also blends of these fibres with themselves or other materials, e.g. wool, nylon, polyester, acetate or acrylic materials.

Application of the reactive dyestuff and fixation on the textile material can be carried out by any method used in practice or known from the literature on the subject prior to the washing step, since the essential difference in the new process lies in avoidance of the customary scouring step. Thus, continuous, semicontinuous or the so-called batchwise methods of application can be used. Furthermore, it is not essential that the dyestuff and alkali be applied to the textile ma terial from a single vessel since it is possible, for example, to impregnate the fabric witha solution of the dyestuff and, with or without an intermediate drying step, thereafter impregnate the material with an alkaline solution, so that only after the second impregnation is the treatment with the dyestuff carried out in the presence of aqueous alkali. Typical methods of application include e.g.: (a) The material may be dyed in the beck, winch or circulatory dyeing machine or on the jig in an aqueous saline solution of dyestuff, the alkali being present from the start or added in one or more portions after a period of time when a part of the dyestuff present has been absorbed by the material. This method is primarily suitable for use with liquor to goods ratios of from 5:1 to 30:1 although ratios outside these limits can be used if desired.

As examples of salts which may be used to make up the saline dyebath, there may be mentioned sodium chloride and sodium sulphate. Salt concentrations of 30 g per litre to g per litre are those most commonly used.

As examples of alkaline substances which are added to the dyestuff solution, there may be mentioned alkali metal hydroxides, silicates, phosphates, carbonates and bicarbonates; in general, the alkali used and the temperature of dyeing may need to be chosen to conform with the cellulose-reactive grouping present in the dye- Reactive group stuff. Typical recommendations are as follows:

Temperature Alkalis dent of depth of shade, typical recommendations being:

These temperatures are those recommended when the alkali is added to the dyebath. With one or two exceptions, notably dichloro-s-triazinylamino, it is possible to carry out impregnation with the dyestuff in neutral or slightly acid solution at up to 130 C, provided that the temperature is lowered to its normal value before adding the alkali. (b) A further method of application comprises padding the material in a dyestuff solution, preferably containing a migration inhibitor, e.g. an alkyl naphthalene sulphonate, a mild oxidising agent e.g. sodium m-nitrobenzene sulphonate, and if necessary, a solubilising agent e.g. urea and then, if desired after an intermediate drying step, immersion of the material in a saline alkaline solution. This second immersion can be carried out e.g. by padding in which case the material may be heated with infra-red heaters, baked or steamed for a short period of time to accelerate the reaction between the dyestuff and the cellulose;

alternatively the immersion may be carried out on the jig or in the winch or beck, in which case the general conditions described under (a) apply. (c) A further method of application comprises padding the material in a dyestuff solution containing the alkali and thereafter heating or steaming as in (b) or wrapping the material in a cover to prevent evaporation and storing the material in a moist condition for a number of hours to effect reaction between the dyestuff and the cellulose. ln this method it is frequently customary to use a stronger alkali than in the methods described under (a). Thus sodium carbonate may be used with dichlorotriazine dyes, a reaction time of 2 hours being usual, whilst dyes containing a group of lower reactivity may be fixed using a caustic alkali or trisodium phosphate and reaction times of 24 hours or longer.

As noted above, the dyeing process differs from those commonly used for application of reactive dyestuffs by omission of the usual scouring step and from those commonly used for application of direct dyes by the concentrations of salt and alkali present in the dye solution.

Since before the advent of reactive dyes, it has been known that the addition of small amounts of sodium carbonate or sodium triphosphate to dyebaths containing direct dyes contributed a useful effect. One such ef feet is to counteract the tendency of many direct dyes to precipitate in hard water or under acid conditions. The latter could arise, e.g. from acid remaining in the textile material from earlier treatments. A second effect is to act to a certain extent as a restraining agent in the case of dyes of high substantivity. The amount of alkali added for these purposes is small and indepena. for padding solutions, used in continuous dyeing,

b. for non-continuous processes, e.g. on the jig or in the winch, from 0.5 to 2% by weight of the material being dyed. In practice, this usually amounts to at most 1 g/l since the smaller quantity would be used at liquorzgoods ratios of 10:1 or less.

In the case of reactive dyes, however, the alkali added takes part in the chemical reaction between the dyestuff and the cellulose molecule and the amount used is frequently related to the strength of dyeing. Thus, for the dyeing of cotton with dichloro-s-triazine dyes, the published recommendations for use of sodium carbonate or sodium triphosphate are:

For monochloro-s-triazine dyes, the published recommendations are:

10 g/l 20 gll continuous dyeing non-continuous dyeing Caustic alkalis, if used in place of carbonates or phosphates can be used in smaller concentrations, e.g. sodium hydroxide is recommended for use at a concen tration of 2 or 2.5 g/l when dyeing on the jig, but more usually is used in continuous or semi-continuous methods at concentrations of 5, 10 or 15 g/l.

The invention may be illustrated by the following Examples in which parts are by weight:

EXAMPLE 1 2,000 parts of water containing 120 parts of salt are heated to C and parts of cotton yarn are added, followed by 2 parts of dyestuff (l) of the Table dissolved in a small amount of water. The yarn is agitated in the dye liquor at 80 C for 30 minutes then 40 parts of sodium carbonate are added and dyeing is continued at 80 C for a further 60 minutes.

The yarn is then removed from the liquor and rinsed in cold water until the rinsing water runs clear. It is dyed in a red shade.

EXAMPLE 2 500 parts of water containing 50 parts of salt are heated to 85 C and 4 parts of dyestuff (2) of the Table are added. 100 parts of viscose rayon piece are added and, after 30 minutes, 10 parts of sodium carbonate are added. After a further 60 minutes, the rayon is removed from the dye liquor and rinsed in water at 3035 C until the rinsings are clear.

The viscose rayon is coloured a deep golden yellow shade.

EXAMPLE 3 EXAMPLE 4 Indian head cotton cloth is padded at 75% expression in a dye liquor containing 13.6 parts of dyestuff (5) of Table l 150 parts of urea 1 1.25 parts of sodium carbonate 1.5 parts of a wetting agent and water to 750 parts. The cloth is dried for 3 minutes at 1 C and baked at 150 C for a further 3 minutes, then given a rinse in cold water.

The cloth is dyed an orange shade.

EXAMPLE 5 Spun viscose rayon piece is padded at expression in a dye liquor containing 27.0 parts of dyestuff (6) of Table l 7.5 parts of sodium carbonate 1.5 parts of a wetting agent and water to 750 parts. The cloth is dried at 1 10 C for 3 minutes and steamed at l00-120 C for 5 minutes, then rinsed in cold water.

The'cloth is dyed an orange shade.

EXAMPLE 6 lndian'head cotton cloth is padded to 75% expression in a dye liquor containing 16.5 parts of dyestuff (4) in Table l 1.5 parts of a wetting agent and water to 750 parts. The cloth is dried for 3 minutes at 1 10 C and further padded in a liquor containing 10 parts of caustic soda 300 parts of salt and water to 1,000 parts. The cloth is steamed, without drying, at -120 C for 1 minute, then rinsed in cold water.

The cloth is dyed a deep golden yellow shade.

The following Table 1 describes the mode of preparing of a number of dyestuffs which can be used in the new process, together with the shade of the resultant dyeings.

rams I 1. Condense 2.4-dichloro-6-aminos-triazine Red with 1 mole of 6-amino-2-(4-phenylazophenylazo)-l-naphthol-2,3,4-trisulphonic acid Condense cyanuric chloride with 1 mole of Golden 4'-nitro-4-( 4 -amino-2"-methylphenylazo )stilbeneyellow 2,2-disulphonic acid and 2 moles of the product with l.4-diaminobenzene-Z-sulphonic acid 3. As for 2. but use benzidine-2,2-disulphonic do.

acid in place of the diaminobenzene sulphonic acid 4. Condense cyanuric chloride with 2-(4"amino-2'- do.

ureidophenylazo)naphthalene-3.6,8-trisulphonic acid and 2 moles of this product with 1,4-diaminohenzene 5. Condense cyanuric chloride with 6-amino-l- Orange hydroxy-2,2 '-azonaphthalenel '.3,5'- trisulphonic acid and 2 moles of the product with l,4-diaminohenzenc-2-sulphonic acid 6. As for 5. but use benzidine-2,2-disulphonic do.

acid in place of the diaminobenzene sulphonic acid 7. Colour lndex Reactive Green 16 Dull bluishgreen 8. Colour lndex Reactive Green 12 Bright yellowishgreen 9. Colour lndex Reactive Red 55 Bluishred Condensc 2.4-dichloro-6-(6',8'- Reddishdisulphonaphth-Z'-ylamino)-$-triazine yellow with 4'-nitro4-(4amino-2"-methylphenylazo)stilbene-2.2'-disulphonic acid Couple tetrazotised 4.4-diaminodiphenylamine- Blue Z-sulphonic acid with 2 moles of 8-(2-chloro- 4'-amino-s-triazin-6'-y1amino)-l-naphthol- 3.6disulphonic acid 12. Condense cyanuric chloride with 1 mole of m- Reddishsulphoaniline and 1 mole of 8-amino-2-l4- blue (3".6". 8"-trisulphonaphth-2-ylazo)-2- methoxy-S-methylphenylazol-l-naphthol-3,6- disulphonic acid Condense cyanuric chloride with 1 mole of 4- Dark nitro-4'-aminostilbene-2 .2'-disulphonic acid brown and 1 mole of 7-anilino-2-(4"aminophenylazo)- l-naphthol-2".3.3'-trisulphonic acid.

[.80. water test of the dyes of Table I when applied to cotton or to viscose rayon by the method of Example 1. The washing test used was I.S.O. No. 3. The results are expressed by reference to the standard geometric grey scales, the first figure being the effect on the dyeing and the second (bracketed) figure being the staining on an adjacent fabric of the same kind as the dyed material.

' g/l sodium chloride:

exhaustion:

Table II gives the results of the test described earlier TABLE IV for these dyestuffs, at the various concentrations of. brine, expressed as a percentage of the dyestuff used. Ex- COTTON VlSCOSE For comparison the table also includes the range incorample 150 3 WATER 3 WATER porated between lines A and B at these concentrations. 5 I 3 (3) 3 (24) (3) 4 (24) In addltlon, Table III provides the figures obtained 2 4 (4) 34(4) 3-4(4-5) from a number of industrially-available reactive and di- 2 2 E2: 2 2 E11 rect dyes indentified by the Colour Index number 5 3 4 3-4 4 4 4-5 3 4 whlch do not conform to the test. In each column of 5 2 gig-3 2 3 6 Tables II and III, the left-hand figure is the exhaustion l 8 4 (34) 2 Z 2 on cotton and the rlght-hand figure 1s the exhaustlon on 9 3 (2) 4 3) 4 (31 viscose. All figures in the tables have been expressed to 10 4 (34) 4 (3 @95 4 the nearest integer. 11 4 34) 413 4-5 4-5) 5 4-51 12 3 4-5) 3-4 3 414-5) 4 3-4) 15 13 3-4 4) 3-4 34) 34 4) 4-5 3-4) TABLE II EXHAUSTION AT VAR ous BRINE CONCENTRATIONS BRINE CONCENTRATION /l) DYESTUFF 0 80 100 120 Table 1 NO. 1 3 1 62 77 77 83 82 87 87 90 89 93 91 Table 1 NO. 2 ll 3 79 74 85 84 88 87 9o 90 93 92 93 92 Table 1 Nb. 3 l1 3 48 44 67 58 75 66 81 73 86 77 88 81 Table 1 N0. 4 3 0 61 59 74 78 81 85 84 88 90 90 92 92 Table 1 No. 5 3 0 49 64 66 79 77 85 84 89 89 92 92 93 Table 1 No.6 2 0 52 43 72 61 84 72 86 79 91 92 92 83 Table 1 No. 7 0 o 46 36 60 70 71 79 80 85 85 88 89 91 Table 1 No. 8 0 o 54 42 68 55 80 66 88 75 93 96 83 Table 1 No.9 3 l 50 47 68 63 77 73 84 78 88 83 91 87 Table 1 N0. 10 11 4 58 63 71 75 79 82 84 87 88 90 91 92 Table 1 NO. 11 7 o 65 70 81 81 90 88 93 90 94 93 96 94 Table 1 No. 12 0 0 38 53 60 74 74 78 83 89 89 93 93 96 Table 1 No. 13 0 0 58 65 75 78 83 87 90 91 94 95 96 96 Range 4-1; 0 15 40 80 55 86 65 90 71 94 75 96 78 97 TABLE III EXHAUSTION AT VARIOUS BRINE CONCENTRATIONS BRINE CONCENTRATION (g/ 1 DYESTUFF Reactive Blue 40 3 3 25 31 36 49 48 59 57 69 67 74 74 80 Reactive Orange 12 5 2 20 27 30 41 36 52 42 62 49 69 56 75 Reactive Red 3 1 0 12 16 19 33 25 38 34 49 38 58 47 65 Reactive Black 5 l 0 7 9 7 15 12 20 16 28 21 32 23 37 Direct Blue 76 63 39 97 94 98 84 95 96 85 91 71 94 59 Direct Red 81 12 3 86 79 93 87 96 73 97 46 95 38 85 30 Direct Yellow 12 21 0 81 77 81 .94 58 42 97 38 96 34 Table IV describesthe fastnesst o washingand to the 50 "wecleiifii l. A process for coloring cellulose textile materials consisting essentially of impregnating the material with a water-soluble dye containing a cellulose-reactive group, fixing the dye on the material by treatment with an alkali applied in the dyebath or a separate bath in an amount conventionally used for that alkali for fixation of cellulose-reactive dyes, said dyestuff used exhibiting the following percentage exhaustions at different saline concentrations when dyed on to cotton or viscose rayon for 60 minutes at a strength of 0.5-1.0%, based on the weight of material being dyed, a liquor-to-goods ratio of 20:1 and a temperature of 80 C:

and rinsing said material after fixation of the dye in 2. A process as claimed in claim 1 wherein the cold water to wash out loose dyestuff and dyebath addicellulose-reactive group present in the dyestuff is a tives. s-triazine group containing a single chlorine atom. 

2. A process as claimed in claim 1 wherein the cellulose-reactive group present in the dyestuff is a s-triazine group containing a single chlorine atom. 